Dihydroazulene-Azobenzene-Dihydroazulene Triad Photoswitches

Photoswitch triads comprising two dihydroazulene (DHA) units in conjugation with a central trans-azobenzene (AZB) unit were prepared in stepwise protocols starting from meta- and para-disubstituted azobenzenes. The para-connected triad had significantly altered optical properties and lacked the photoactivity of the separate photochromes. In contrast, for the meta-connected triad, all three photochromes could be photoisomerized to generate an isomer with two vinylheptafulvene (VHF) units and a cis-azobenzene unit. Ultrafast spectroscopy of the photoisomerizations revealed a fast DHA-to-VHF photoisomerization and a slower trans-to-cis AZB photoisomerization. This meta triad underwent thermal VHF-to-DHA back-conversion with a similar rate of all VHFs, independent of the identity of the neighboring units, and in parallel thermal cis-to-trans AZB conversion. The experimental observations were supported by computation (excitation spectra and orbital analysis of the transitions).     

A Toroidal Zr70 Oxysulfate Cluster and Its Diverse Packing Structures

Herein, we report the discovery of a toroidal inorganic cluster of zirconium(IV) oxysulfate of unprecedented size with the formula Zr₇₀(SO₄)₅₈(O/OH)₁₄₆⋅x(H₂O) (Zr₇₀), which displays different packing of ring units and thus several polymorphic crystal structures. The ring measures over 3 nm across, has an inner cavity of 1 nm and displays a pseudo-10-fold rotational symmetry of Zr₆ octahedra bridged by an additional Zr in the outer rim of the ring. Depending on the co-crystallizing species, the rings form various crystalline phases in which the torus units are connected in extended chain and network structures. One phase, in which the ring units are arranged in layers and form one-dimensional channels, displays high permanent porosity (BET surface area: 241 m² g⁻¹), and thus demonstrates a functional property for potential use in, for example, adsorption or heterogeneous catalysis.     

Comparison of single-phase and two-phase measurements in extraction,separation and back-extraction of Cd,Zn and Co from a multi-element matrix using Aliquat 336

Journal of Radioanalytical and Nuclear Chemistry - Cd and Zn were separated from Co, from chloride solutions containing 16 different metal ions. The separation method used was liquid–liquid...     

Synthesis of dithiafulvene–quinone donor–acceptor systems: isolation of a Michael adduct

π‐Conjugated donor–acceptor systems based on dithiafulvene (DTF) donor units and various acceptor units have attracted attention for their linear and nonlinear optical properties. The reaction between p‐benzoquinone and a 1,3‐dithiole phosphonium salt, deprotonated by lithium hexamethyldisilazide (LiHMDS), gave a product mixture from which the Michael adduct [systematic name: dimethyl 2‐(3‐hydroxy‐6‐oxocyclohexa‐2,4‐dien‐1‐ylidene)‐2H‐1,3‐dithiole‐4,5‐dicarboxylate], C₁₃H₁₀O₆S₂, was isolated. It is likely that one of the unidentified products obtained previously by others from related reactions could be a similar Michael adduct.     

Dimensional analysis of pore scale and field scale immiscible displacement

A basic re-examination of the traditional dimensional analysis of microscopic and macroscopic multiphase flow equations in porous media is presented. We introduce a macroscopic capillary number which differs from the usual microscopic capillary number Ca in that it depends on length scale, type of porous medium and saturation history. The macroscopic capillary number is defined as the ratio between the macroscopic viscous pressure drop and the macroscopic capillary pressure. can be related to the microscopic capillary number Ca and the LeverettJ-function. Previous dimensional analyses contain a tacit assumption which amounts to setting = 1. This fact has impeded quantitative upscaling in the past. Our definition for , however, allows for the first time a consistent comparison between macroscopic flow experiments on different length scales. Illustrative sample calculations are presented which show that the breakpoint in capillary desaturation curves for different porous media appears to occur at 1. The length scale related difference between the macroscopic capillary number for core floods and reservoir floods provides a possible explanation for the systematic difference between residual oil saturations measured in field floods as compared to laboratory experiment.     

Raman endoscopy for in vivo differentiation between benign and malignant ulcers in the stomach

The aim of this study was to evaluate the clinical utility of an image-guided Raman endoscopy technique for in vivo differential diagnosis of benign and malignant ulcerous lesions in the stomach. A rapid-acquisition image-guided Raman endoscopy system with 785 nm laser excitation has been developed to acquire in vivo gastric tissue Raman spectra within 0.5 s during clinical gastroscopic examinations. A total of 1102 in vivo Raman spectra were acquired from 71 gastric patients, in which 924 Raman spectra were from normal tissue, 111 Raman spectra were from benign ulcers whereas 67 Raman spectra were from ulcerated adenocarcinoma. There were distinctive spectral differences in Raman spectra among normal mucosa, benign ulcers and malignant ulcers, particularly in the spectral ranges of 800-900, 1000-1100, 1245-1335, 1440-1450 and 1500-1800 cm(-1), which primarily contain signals related to proteins, DNA, lipids and blood. The malignant ulcerous lesions showed Raman signals to be mainly associated with abnormal nuclear activity and decrease in lipids as compared to benign ulcers. Partial least squares-discriminant analysis (PLS-DA) was employed to generate multi-class diagnostic algorithms for classification of Raman spectra of different gastric tissue types. The PLS-DA algorithms together with leave-one tissue site-out, cross validation technique yielded diagnostic sensitivities of 90.8%, 84.7%, 82.1%, and specificities of 93.8%, 94.5%, 95.3%, respectively, for classification of normal mucosa, benign and malignant ulcerous lesions in the stomach. This work demonstrates that image-guided Raman endoscopy technique associated with PLS-DA diagnostic algorithms has for the first time promising clinical potential for rapid, in vivo diagnosis and detection of malignant ulcerous gastric lesions at the molecular level.     

Quantifying electronic effects of common carbohydrate protecting groups in a piperidine model system

A study of the substituent effects of protecting groups in hydroxypiperidines was carried out and compared with the electronic effects in glycosylation chemistry. 1‐Deoxynojirimycin, the aza‐sugar analogue of 1‐deoxy‐D ‐glucose, was used as a carbohydrate model, and protected with the most common carbohydrate protecting groups. The different stabilization of positive charge on the ring heteroatom was determined by pK_a measurements. The protecting groups could be ranked in the following way after their destabilization of the piperidinium ion: benzoyl≥acetyl?4,6‐O‐benzylidine>benzyl≈methyl>H>3,6‐anhydro>tert‐butyldimethylsilyl. The observed effects of having protecting groups with different electronic characteristics were found to be in agreement with the “armed–disarmed” concept. Comparison of the pK_a of benzylated and benzoylated epimers of 3‐hydroxy‐6‐hydroxymethyl piperidines showed increased stabilization of the piperidinium ion in the axial epimer. The difference between axial and equatorial epimers was larger in the benzylated than in the benzoylated piperidines.     

Single crystals of L-O-serine phosphate X-irradiated at low temperatures: EPR, ENDOR, EIE, and DFT studies

Single crystals of the phosphorylated amino acid L-O-serine phosphate were X-irradiated and studied at 10 K and at 77 K using EPR, ENDOR, and EIE techniques. Two radicals, R1(10 K) and R1(77 K), were detected and characterized as two different geometrical conformations of the protonated reduction product >CH-C(OH)(2). R1(10 K) is only observed after irradiation at 10 K, and upon heating to 40 K, R1(10 K) transforms rapidly and irreversibly into R1(77 K). The transition from R1(10 K) to R1(77 K) strongly increases the isotropic hyperfine coupling of the C-CH(beta) coupling (Delta = 32 MHz) and the major C-OH(beta) coupling (Delta = 47 MHz), in sharp contrast to the their much reduced anisotropic hyperfine couplings after the transition. An umbrella-like inversion of the carboxylic acid center, accompanied by minor geometrical adjustments, explains the changes of these observed isotropic and anisotropic couplings. DFT calculations were done on the reduced and protonated L-O-serine phosphate radical at the B3LYP/6-311+G(2df,p)//B3LYP/6-31+G(d) level of theory in order to support the experimental observations. Two different conformations of the anion radical, related by an inversion at the carboxylic center, could be found within the single molecule partial energy-optimization scheme. These two conformations reproduce the experimental hyperfine couplings from radicals R1(10 K) and R1(77 K). A third radical, radical R2, was observed experimentally at both 10 and 77 K and was shown to be due to the decarboxylated L-O-serine phosphate oxidation product, a conclusion fully supported from the DFT calculations. Upon thermal annealing from 77 to 295 K, radicals R1(77 K) and R2 disappeared and all three previously observed room-temperature radicals could be observed. No phosphate-centered radicals could be observed at any temperatures, indicating that the phosphate-ester bond break for one of the room-temperature radicals does not occur by dissociative electron capture at the phosphate group.     

Constructing tilted algebras from cluster-tilted algebras

Any cluster-tilted algebra is the relation extension of a tilted algebra. Given the distribution of a cluster-tilting object in the Auslander–Reiten quiver of the cluster category, we present a method to construct all tilted algebras whose relation extension is the endomorphism ring of this cluster-tilting object.     

Identification and characterization of a bacterial glutamic peptidase

Background  

Glutamic peptidases, from the MEROPS family G1, are a distinct group of peptidases characterized by a catalytic dyad consisting of a glutamate and a glutamine residue, optimal activity at acidic pH and insensitivity towards the microbial derived protease inhibitor, pepstatin. Previously, only glutamic peptidases derived from filamentous fungi have been characterized.